Process of treating hydrocarbon-oils.



T. T. GRAY.

PRocEss of HEATING 'HYDRocARoN ons. APPLICATION FILED DEC. 3. 1913.

1,158,205. ,mined 001;. 26, 1915.

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THOMAS T. GRAY, OF ELIZABETH, NEW JERSEY.

PROCESS OF TREATING HYDROCARBON-OILS.

Specicationof Letters Patent.

Patented Oct. 26, 1915.

Application led December 3,y 1913. Serial No. 804,467.

Elizabeth, in thecounty of Union and State of New Jersey, have invented certain new and useful Improvements. in Processes of Treating Hydrocarbon-Oils, fof Whichvthc following is a'specilication.

This invention relates to treatinghydrocarbon oils, such as petroleum distillates and residues or distillates from other carbonaceous material, as lignite, shale, etc., and including paraffin wax, for improving thequality and obtaining useful products.

The hydrocarbon oils now generally found in the market possess the quality of fluorescence. This quality is objectionable and the trade now demands hydrocarbon oils for certain purposes, especially lubricating oils, which are free from fluorescence. I have therefore devised ,a process of treating fiuorescent oils which I term deblooming, and which results in completely removing the objectionable fluorescence.

I have discovered that when hydrocarbon oils are subjected to oxygenation as by currents of air, oxygen or an oxygen-carrying of deblooming will be most gas orvapor, in the presence, and under the influence of ultra violet light, the operation efficiently and rapidly effected. I have also discovered that these same active'rays greatly accelerate the conversion of hydrocarbons-When blown with an oxygen carrying gas or vapor, into fatty acids and organic esters. In carrying out my process, therefore, I suspend or place in the still or treating chamber a number of lamps giving ultra violet rays, so that suchl rays shall be directed at close range upon the body of oil being treated. For the purpose of oxygenating the oil, I may blow air or an oxygen carrying gas or vapor in numerous streams up through the body of oil. The process may in some cases be advantageously conducted under pressure of one to live atmospheres in the treating chamber or still. In case of' rendering oils non-fiuorescent a lower temperature may be used, from 50 to 120 C., depending upon the nature of the product being treated. For converting the hydrocarbons into fatty acids and esters, a higher temperature of 90 to 175 C. or 250 F. to 300 F. may be maintained in the still, according to the character'of the hydrocarbons being treated.r

and their susceptibility to oxygenation and esterilication,

'u have found that the process may be facilitated by carrying out the operations in the presence of catalytic agents or porous contact material consisting of .metals, or finely divided or reduced metals, or their bases, or salts, or porous granular or absorbent materials, or porous, granular, or absorbent material `carrying finely divided or reduced metals, their salts or bases. The catalytic agent or contact material 'may be carried in al layer on a perforated tray orA grid in the still or treating chamber.

The matter constituting my invention will be defined in the claims.

' j Suitable apparatus for carrying out my process is illustrated in the accompanying drawing, which represents a vertical longitudinal section of the apparatus with parts in elevation.

A cylindrical form of still or treating chamber A is supported on a foundation X, and is preferably covered with non-conducting or insulating material y, since it is to be heated by an 'interior steam coil. The still is provided with the usualdome/ a., from which leads a vapor discharge pipe C to a condenser coil C in a water tank H. To the vapor pipe may be applied a pop safety valve a', a stop valve a, and a pressurecontrolling valve la, which may be set at any desired pressure for controllingthe degree of pressure in the still. The discharge end of coil C is provided with a valve @,and tank H is provided with valved' water supply and drain pipesas shown. A pressure gage g ispreferably applied to the tp of the still. An air supply pipe B, having a valve b, may lead from a compressor and extends down to near. the bottom of the still where connection is made with one or more perforated distributing pipes B', extending longitudinally nearly the length of the still.

high pressure steam supply pipe E, having a valve e, extends through the wall of the still and connects with a heating coil E located near the bottom but above the airdistributing pipe, and having an escape pipe e. extending out through the wall of the still. An oil supply pipe F, having a valve f, extends down into the still. A draw-.olf pipe, P, having a valve p, may connect with the bottom of the still.

A horizontal perforated tray or grid D I so' is located inthe still at a suitable distance above the steam coil for supporting a layer of catalytic agent or contact material d. Two or more of such trays may be used if desired. A

Any-desired number of lamps J, giving ultra violet rays, are connected by electric conductors Z passing through insulators n and suspended from the top of the still. -In the position shown they will effectively shed their active rays upon the surface of the Vbody of' oil under treatment and perform their desired function in my process.

The oil to be treated is supplied through pipe F by a pump or other means, suitable body is formed as indicated in the drawing. In case paraffin wax is to be treated it may be first melted and then run into theL still through pipe F. High pressure steam is admitted to the heating coil E', and the body of oil or melted paraffin wax heated to. the desired temperature. he electric current is turned on to the lamps J. Air or other oxygen carrying gas or vapor will now be blown in numerous streams through the perforated pipe B, and such streams will agitate the oil, or melted paraffin wax, so that fresh'portions of hydrocarbons will be continuously exposed to the ac-l ti've rays-of the lamps. For the purpose of rendering the oil non-fluorescent a temperature is maintained from 50 to 120 C. The length of time required for treatment will depend upon the hydrocarbons being treated and their susceptibility to oxygenation. The process is continued until 'a sample drawn from the still shows the oil to be debloomed or made non-fluorescent; then the operation is complete and the contents may be drawn from the still. In case the hydrocarbon is to be converted into fatty acids and esters, the temperature must be raised to a suitable degree between 250 F. and 300 F., depending upon the character of. the oil being treated andits susceptibility to oxygenation and esterication. The process will also be extended over a longer period of time than that required for removing fluorescence. I have been able by this process i a quantity of hydrocarbons into fatty acids. Samples taken from the still will show the progress being made in the production of fatty acids. I have demonstrated by numerous tests that the ultra violet rays of the lamps exercise a very.beneficial influence in my process and greatly accelerate the deblooming and conversion of the hydrocarbons into fatty acids and esters, and also, in1 some cases, -of bleaching the color of the o1 The following is stated as a furtherfillustration of how hydrocarbon cils or p/araffin wax may be treated in order to remove fluorescence and to form` fatty acids and till a to convert seventy-five per cent. of-

lorganic esters: rI`he oil or wax is contained in a receptacle, over which is placedjalamp giving the ultra violet light. The small tank receptacle may be either open or closed and contains a tight coil immersed in oil for heating or cooling; incase the oil is to be heated, stea is allowed to pass through the coil, and in case it is to be cooled Water is passed through. The receptacle contains in addition, a perforated coil through which air, or oxygen, or ozone, or an oxygen-carrying gas vapor is passed to agitate the oi'l and at the same time to oxidize the compounds giving fluorescence. T he lamp is placed as near to the oil as possible, allowing for the agitation; that is, the lamp is preferably placed within surface of the oil. The temperature for deblooming should not exceed 100 C., otherwise discoloration of the oil will be brought about, making the oil unfit for use without further refining by ordinary refining methods to remove this dark color. In case the temperature should rise above 100 C., water is passed through the coil until the lthermometer reading shows lower than 100 C. As a rule the radiation of the lamp will give enough heat for this purpose. Working in this way with a lamp giving a voltage of 220, placed four inches from the surface of the oil, which was agitated gently with air or oxygen, in the case of air it required approximately eight hours to debloom a depth of three inches covering a surface one foot square per lamp. In case of a closed apparatus, there would naturally have to be a vent for air or oxygen relief. The process takes place quickly and is very apparent when samples are drawn 0E at the bottom and observed by reflected light.

In case of forming esters higher temperatures are necessary, and the process can be effectively carried out in the same apparatus. takes place by this processand fatty acids and esters are formed. "The ordinary working temperatures to' bring about this reaction are preferably between 100 and 200 C. In order to lind out the rate at which orfiganic esters are formed, a sample is drawn o and the amount of unsaponifiablematter is determined as described in Lefwlcowtsch, 3rd edition, volume 1, page 293. The unsaponiable matter will be the unacted upon oil or wax and alcohols and the saponifiable matter will be the difference and Will illustrate the stage of the process. With practice, the determination of value as described in the same volume of Lewcmnitsch cited above, page 226, will serve as an index of the extent to which the hydrofrom two to six inches of the the saponification fatty acids or organic Debloomlngl I carbons have been converted into saponifithe saponiicaticn value reaches 200. When the proper saponiication value is reached the oil or Wax is Withdrawn from the appa` ratus. Enough air, oroxygen, or oxygencarrying gas or vapor, including ozone, is

used to agitate the oil or Wax vand bringA fresh layers in contact with the ultra-violet;

rays. y

Caustic soda or caustic potash aresuitable catalytic agents, and may be used'up to 20 per cent. of the Weight 0f the oil.

bottom of the treating vessel or on a tray near the bottom. i Having ydescribed my invention, what I claim and desire to secure by Letters Patent, is:

l. The process of deblooming hydrocarbons and converting them into fatty acids and esters, which consists in subjecting them to an oxidizing agent in the presence of ultra violet or active rays.

2. The process of treating hydrocarbons for deblooming. and forming fatty acids and esters, which consists in subjecting them Ato an oxidizing agent in a heated condition and in the presence of ultra violet or active rays.

3. The process of treating hydrocarbons for deblooming and forming fatty acids and esters, which consists in subjecting them to an oXidizinga-gent in the presence of ultra violet or active rays and in the presence of a. catalytic or contact agent.

4. The process of treating hydrocarbons for deblooming and forming fatty acids and esters, which consists in subjecting them to an oxidizing agent in a heated condition in the presence of ultra violet or active rays, and of a catalytic or contact agent such as finely divided or reduced metals, their salts or bases, porous, granular or absorbent material, or such materials carrying finely divided or reduced metals, their bases or Salts.

5. The process of treating hydrocarbons for deblooming and forming fatty acids and 'for' The catalytic 'agents 1n each case areV placed in the.V

esters, vvhich consists in subjecting them t` p'ressure'andan oxidizing agent in the presence of` ultra'-.vio1et or active rays.

6.y The'process of treating hydrocarbons debloomingand forming fatty acids and esters, Whichconsists in heating them and subjecting to pressure and an oxidizing agent inthe presence of ultra violet'- or active ra s.

l. The process of treating hydrocarbons for deblooming and formingfatty acids and e's'tes, which consists in subjecting them to l pressure and an oxidizing agent inthe presence of ultra violet or active rays and in the presence of a catalytic or contact agent.

desired temperature, blowing streams of` oxygen-carrying gas, or vapor'through the' mass 1n the presence of ultra violet or active rays.

10. The process of treatinghydrocarbon-s for deblooming and forming fatty acids and esters, which' consists in heating them, blovv-V p ing streams o f oxygen-carrying gas or vapor l through' the mass in thepresence of ultra violetoractive rays and 1n the presence of a catalytic or contact agent.

11. The process of treating hydrocarbons for deblooming, and bleaching them which consists in subjecting them to an oxidizing agent in the presence of ultra-violet or active ra s.

ln testimony whereof I aix my signature in presence of two witnesses. l

THOMAS T. GRAY. Witnesses WALTER MILLER, HARRY R. JosTnN. 

